Silicone polyoxamide copolymers

ABSTRACT

Silicone polyoxamide and silicone polyoxamide-hydrazide copolymers comprise at least two repeating units of formula (I). In this formula, each R1 is independently an alkyl, haloalkyl, aralkyl, alkenyl, aryl, or aryl substituted with an alkyl, alkoxy, or halo; each Y is independently an alkylene, aralkylene, or a combination thereof; each G is independently a bond or a divalent residue equal to a diamine of formula R3HN-G-NHR3 minus the two —NHR3 groups; each R3 is independently hydrogen or alkyl or R3 taken together with G and with the nitrogen to which they are both attached form a heterocyclic group; each n is independently an integer of 0 to 300; each p is independently an integer of 1 to 25, and the average of p is 1.3 or greater; and each q is independently an integer of 1 to 2, and the average of q is no greater than 1.05.

RELATED CASE

This case is related to a copending provisional application assigned tothe present assignee entitled SILICONE POLYOXAMIDE COPOLYMERS WITHAMINE-BASED END GROUPS, U.S. provisional application 62/950,806, filedDec. 19, 2019, the contents of which is incorporated in its entirety.

BACKGROUND SUMMARY

Siloxane polymers have unique properties derived mainly from thephysical and chemical characteristics of the siloxane bond. Theseproperties include low glass transition temperature, thermal andoxidative stability, resistance to ultraviolet radiation, low surfaceenergy and hydrophobicity, high permeability to many gases, andbiocompatibility. The siloxane polymers, however, often lack tensilestrength.

The low tensile strength of the siloxane polymers can be improved byforming block copolymers. Some block copolymers contain a “soft”siloxane polymeric block or segment and any of a variety of “hard”blocks or segments. Polydiorganosiloxane polyamides,polydiorganosiloxane polyureas, and polydiorganosiloxane polyoxamidecopolymers are exemplary block copolymers.

Polydiorganosiloxane polyamides have been prepared by condensationreactions of amino terminated silicones with short-chained dicarboxylicacids. Alternatively, these copolymers have been prepared bycondensation reactions of carboxy terminated silicones withshort-chained diamines. Because polydiorganosiloxanes (e.g.,polydimethylsiloxanes) and polyamides often have significantly differentsolubility parameters, it can be difficult to find reaction conditionsfor production of siloxane-based polyamides that result in high degreesof polymerization, particularly with larger homologs of thepolyorganosiloxane segments. Many of the known siloxane-based polyamidecopolymers contain relatively short segments of the polydiorganosiloxane(e.g., polydimethylsiloxane) such as segments having no greater than 30diorganosiloxy (e.g., dimethylsiloxy) units or the amount of thepolydiorganosiloxane segment in the copolymer is relatively low. Thatis, the fraction (i.e., amount based on weight) of polydiorganosiloxane(e.g., polydimethylsiloxane) soft segments in the resulting copolymerstends to be low.

Polydiorganosiloxane polyoxamides such as those disclosed in U.S. Pat.No. 7,501,184 (Leir et al.) are yet another type of block copolymer.Known polydiorganosiloxane polyoxamide copolymers have been made bymixing a diamine such as ethylene diamine with a precursor that includesat least one polydiorganosiloxane segment and at least two oxalylaminogroups. The resulting copolymers have alternating softpolydiorganosiloxane segments (S) and hard oxamide segments (H) (i.e.,the copolymers are of a (S-H)_(n) type). These polydiorganosiloxanepolyoxamide copolymers thus contain a relatively large fraction of thepolydiorganosiloxane segment compared to many known polydiorganosiloxanepolyamide copolymers. Such polydiorganosiloxane polyoxamide copolymerscan usually be subjected to elevated temperatures up to 250° C. orhigher without apparent degradation.

Additional polydiorganosiloxane polyoxamide copolymers are described inU.S. Pat. Nos. 7,981,995 and 8,124,713 (Hays et al.). Suchpolydiorganosiloxane polyoxamides copolymers feature a more randomdistribution of hard segments (H) between soft segments (S), with theextra “runs” of hard segments providing improved properties in thedescribed applications.

In view of the foregoing, the present inventors recognize that althoughthe alternating soft and hard segment polydiorganosiloxane polyoxamidecopolymers described above are an improvement over less thermally stablethermoplastic silicone elastomers, it would be advantageous to have theability to firmly control the distribution of hard segments within thecopolymer chain, while expediting or excising process steps thoughtnecessary to create such copolymers. Furthermore, the performance of theresulting copolymers in certain adhesive compositions could be enhancedby “capping” an intermediate structure with desired end groups, allowingfor additional application tailoring, as described in applicant'sco-pending application entitled “SILICONE POLYOXAMIDE COPOLYMERS WITHAMINE-BASED END GROUPS”, attorney matter number 82293US002.

Briefly, in one aspect, the present disclosure provides siliconepolyoxamide and silicone polyoxamide-hydrazide copolymers comprising atleast two repeating units of formula I:

In this formula, each R¹ is independently an alkyl, haloalkyl, aralkyl,alkenyl, aryl, or aryl substituted with an alkyl, alkoxy, or halo; eachY is independently an alkylene, aralkylene, or a combination thereof,each G is independently a bond or a divalent residue equal to a diamineof formula R³HN-G-NHR³ minus the two —NHR³ groups; each R³ isindependently hydrogen or alkyl or R³ taken together with G and with thenitrogen to which they are both attached form a heterocyclic group; eachn is independently an integer of 0 to 300; each p is independently aninteger of 1 to 25, and the average of p is 1.3 or greater; and each qis independently an integer of 1 to 2, and the average of q is 1.05 orless.

The silicone polyoxamide and silicone polyoxamide-hydrazide copolymershave both hard segments and soft segments. The soft segments arecontributed by the silicone-based amines that have apolydiorganosiloxane segment p. The hard segments are contributed by theoxamide group containing segment q.

In another aspect, the present disclosure provides a method of making acopolymeric material comprising at least two repeat units of formula I′:

wherein R¹, Y, G, R³, n, p, and q are defined as above.

The method comprises (a) adding an oxalate ester of formula II to asolvent

wherein each R² is independently an alkyl, haloalkyl, aryl, or arylsubstituted with an alkyl, alkoxy, halo, alkyoxycarbonyl, or

bound through the N, wherein each R⁴ is independently hydrogen, alkyl,or aryl or R⁴ taken together form a ring; (b) reacting apolydiorganosiloxane diamine of formula III until essentially no oxalateester remains

to form the reaction product of formula IV

and (c) adding one or more diamines of formula V to the reaction productof formula IV to form the repeat unit of formula I′

Previously known methods of making polydiorganosiloxane polyoxamidecopolymers such as the methods disclosed in U.S. Pat. No. 7,501,184(Leir et al.), U.S. Pat. Nos. 8,764,881, 7,981,985, and 8,124,713 (Hayset al.) can require a costly excess of oxalate, demand recrystallizationat certain steps, or can result in undesirable rheologicalcharacteristics for mounting and other adhesive applications. Themethods of the present disclosure, however, can be used to makecopolymers particularly well suited for use in pressure sensitiveadhesives and mounting articles, with fewer steps and raw materialamounts needed to create the copolymers.

The present disclosure further provides adhesive compositions includingthe silicone copolymers described above. Adhesive compositions of thepresent disclosure can include a silicone polyoxamide copolymer orsilicone polyoxamide-hydrazide copolymer, a tackifying resin, andoptionally filler. The adhesive compositions can be at least one ofpressure sensitive and heat-activated, as those terms are defined below.In some embodiments, the adhesive composition includes at least one of asilicone polyoxamide or silicone polyoxamide-hydrazide copolymer, asilicate tackifying resin, and optionally inorganic particle filler. Theadhesive compositions may be stretch release or peel release and may bedamage-free.

DETAILED DESCRIPTION

The silicone polyoxamide and silicone polyoxamide-hydrazide copolymersof the disclosure comprise at least two repeating units of formula I:

In this formula, each R¹ is independently an alkyl, haloalkyl, aralkyl,alkenyl, aryl, or aryl substituted with an alkyl, alkoxy, or halo; eachY is independently an alkylene, aralkylene, or a combination thereof,each G is independently a bond or a divalent residue equal to a diamineof formula R³HN-G-NHR³ minus the two —NHR³ groups; each R³ isindependently hydrogen or alkyl or R³ taken together with G and with thenitrogen to which they are both attached form a heterocyclic group(e.g., R³HN-G-NHR³ is piperazine or the like); each n is independentlyan integer of 0 to 300; each p is independently an integer of 1 to 25,and the average of p is 1.3 or greater; and each q is independently aninteger of 1 to 2, and the average of q is 1.05 or less.

Suitable alkyl groups for R¹ in formula I typically have 1 to 10, 1 to6, or 1 to 4 carbon atoms. Exemplary alkyl groups include, but are notlimited to, methyl, ethyl, isopropyl, n-propyl, n-butyl, and iso-butyl.Suitable haloalkyl groups for R¹ often have only a portion of thehydrogen atoms of the corresponding alkyl group replaced with a halogen.Exemplary haloalkyl groups include chloroalkyl and fluoroalkyl groupswith 1 to 3 halo atoms and 3 to 10 carbon atoms. Suitable alkenyl groupsfor R¹ often have 2 to 10 carbon atoms. Exemplary alkenyl groups oftenhave 2 to 8, 2 to 6, or 2 to 4 carbon atoms such as ethenyl, n-propenyl,and n-butenyl. Suitable aryl groups for R¹ often have 6 to 12 carbonatoms. Phenyl is an exemplary aryl group. The aryl group can beunsubstituted or substituted with an alkyl (e.g., an alkyl having 1 to10 carbon atoms, 1 to 6 carbon atoms, or 1 to 4 carbon atoms), an alkoxy(e.g., an alkoxy having 1 to 10 carbon atoms, 1 to 6 carbon atoms, or 1to 4 carbon atoms), or halo (e.g., chloro, bromo, or fluoro). Suitablearalkyl groups for R¹ usually have an alkylene group with 1 to 10 carbonatoms and an aryl group with 6 to 12 carbon atoms. In some exemplaryaralkyl groups, the aryl group is phenyl and the alkylene group has 1 to10 carbon atoms, 1 to 6 carbon atoms, or 1 to 4 carbon atoms (i.e., thestructure of the aralkyl is alkylene-phenyl where an alkylene is bondedto a phenyl group).

In some embodiments, in some repeat units of formula I, at least 40percent, and preferably at least 50 percent, of the R¹ groups aremethyl. For example, at least 60 percent, at least 70 percent, at least80 percent, at least 90 percent, at least 95 percent, at least 98percent, or at least 99 percent of the R¹ groups can be methyl. Theremaining R¹ groups can be selected from an alkyl having at least twocarbon atoms, haloalkyl, aralkyl, alkenyl, aryl, or aryl substitutedwith an alkyl, alkoxy, or halo.

Each Y in formula I is independently an alkylene, aralkylene, or acombination thereof. Suitable alkylene groups typically have up to 10carbon atoms, up to 8 carbon atoms, up to 6 carbon atoms, or up to 4carbon atoms. Exemplary alkylene groups include methylene, ethylene,propylene, butylene, and the like. Suitable aralkylene groups usuallyhave an arylene group with 6 to 12 carbon atoms bonded to an alkylenegroup with 1 to 10 carbon atoms. In some exemplary aralkylene groups,the arylene portion is phenylene. That is, the divalent aralkylene groupis phenylene-alkylene where the phenylene is bonded to an alkylenehaving 1 to 10, 1 to 8, 1 to 6, or 1 to 4 carbon atoms. As used hereinwith reference to group Y, “a combination thereof” refers to acombination of two or more groups selected from an alkylene andaralkylene group. A combination can be, for example, a single aralkylenebonded to a single alkylene (e.g., alkylene-arylene-alkylene). In oneexemplary alkylene-arylene-alkylene combination, the arylene isphenylene and each alkylene has 1 to 10, 1 to 6, or 1 to 4 carbon atoms.

Each G in formula I is independently a bond or a residual unit that isequal to a diamine compound of formula R³HN-G-NHR³ minus the two aminogroups (i.e., —NHR³ groups). When G is a bond, the copolymer is asilicone polyoxamide-hydrazide. In some embodiments, G is a bond andeach R³ is hydrogen.

When G is a residual unit, the copolymer is a silicone polyoxamide. Thediamine can have primary or secondary amino groups. Group R³ is hydrogenor alkyl (e.g., an alkyl having 1 to 10, 1 to 6, or 1 to 4 carbon atoms)or R³ taken together with G and with the nitrogen to which they are bothattached forms a heterocyclic group (e.g., R³HN-G-NHR³ is piperazine).In most embodiments, R³ is hydrogen or an alkyl. In many embodiments,both of the amino groups of the diamine are primary amino groups (i.e.,both R³ groups are hydrogen) and the diamine is of formula H₂N-G-NH₂.

In some embodiments, G is an alkylene, heteroalkylene, arylene,aralkylene, or a combination thereof. Suitable alkylenes often have 2 to10, 2 to 6, or 2 to 4 carbon atoms. Exemplary alkylene groups includeethylene, propylene, butylene, and the like. Suitable heteroalkylenesare often polyoxyalkylenes such as polyoxyethylene having at least 2ethylene units, polyoxypropylene having at least 2 propylene units, orcopolymers thereof. Suitable aralkylene groups usually contain anarylene group having 6 to 12 carbon atoms bonded to an alkylene grouphaving 1 to 10 carbon atoms. Some exemplary aralkylene groups arephenylene-alkylene where the phenylene is bonded to an alkylene having 1to 10 carbon atoms, 1 to 8 carbon atoms, 1 to 6 carbon atoms, or 1 to 4carbon atoms. As used herein with reference to group G, “a combinationthereof” refers to a combination of two or more groups selected from analkylene, heteroalkylene, arylene, and aralkylene. A combination can be,for example, an aralkylene bonded to an alkylene (e.g.,alkylene-arylene-alkylene). In one exemplary alkylene-arylene-alkylenecombination, the arylene is phenylene and each alkylene has 1 to 10, 1to 6, or 1 to 4 carbon atoms.

Each subscript n in formula I is independently an integer of 0 to 300.For example, subscript n can be an integer up to 275, up to 250, up to200, up to 100, up to 80, up to 60, up to 40, up to 20, or up to 10. Thevalue of n is often at least 1, at least 2, at least 3, at least 5, atleast 10, at least 20, or at least 40. For example, subscript n can bein the range of 40 to 300, 1 to 300, 1 to 200, 1 to 100, 1 to 80, 1 to40, or 1 to 20.

Each subscript p is independently an integer of 1 to 25. For example,the value of p is often an integer up to 9, up to 8, up to 7, up to 6,up to 5, up to 4, up to 3, or up to 2. The value of p can be in therange of 1 to 8, 1 to 6, or 1 to 4. The average of p is 1.3 or greater.

The soft segments (p) tend to be present in the copolymer of Formula Iat a multi-modal distribution of number average molecular weights.

Each subscript q is independently an integer of 1 to 2, andsubstantially every q is 1. In some embodiments, each subscript q is aninteger of 1. The average of q is 1.05 or less. Without wishing to bebound by theory, an average q of 1.05 or less limits the number ofcrosslinks in the hard segment, maintaining the copolymers of thepresent disclosure below the gel point. The use of such copolymers inadhesive compositions can result in at least one of enhanced shearstrength and improved peel adhesion to target adherends.

Failing to keep q at an average of 1.05 or less can result in too manyruns (i.e., where q is 2 or more) of hard segments, leading to overlystiff and less desirable adhesive compositions for certain applications.Such compositions may be insufficiently tacky and/or may notsufficiently wet out on surfaces. An adhesive composition featuring anaverage of q greater than 1.05 might be particularly undesirable formounting applications described in more depth below.

The value of q and p can be controlled by the ratio of components usedto prepare the precursor of formula IV below in the creation of thecopolymers of formula I′. A sufficient molar amount of amino groups inthe polydiorganosiloxane diamine of formula III of (e.g., the amountneeded to achieve a molar ratio with the oxalate ester compound offormula II of at least 0.56:1) tends to favor the formation ofprecursors of formula IV that, when forwarded to copolymers of formulaI′, result in the substantial majority of the compounds having q equalto 1 (i.e., such that the average of q is 1.05 or less). Moreover, amolar ratio (i.e., stoichiometric ratio) of silicone amine to oxalateester of at least 0.56:1 can help ensure that p is greater than or equalto 1.3.

The molar ratio of total amine to oxalate ester in the copolymers offormula I is typically about 0.96:1.04. The copolymers of the disclosuretend to be free of groups having a formula —R^(a)—(CO)—NH— where R^(a)is an alkylene. All or nearly all of the carbonylamino groups along thebackbone of the copolymeric material are part of an oxalylamino group(i.e., the —(CO)—(CO)—NH— group). That is, any carbonyl group along thebackbone of the copolymeric material is bonded to another carbonyl groupand is part of an oxalyl group. More specifically, the copolymers of thedisclosure have a plurality of aminoxalylamino groups.

The silicone polyoxamide and silicone polyoxamide-hydrazide copolymersof the disclosure (and other silicone polyoxamide and siliconepolyoxamide-hydrazide copolymers) can be prepared according the methodof the disclosure. The following method can be used to make acopolymeric material comprising at least two repeat units of formula I′:

wherein each R¹ is independently an alkyl, haloalkyl, aralkyl, alkenyl,aryl, or aryl substituted with an alkyl, alkoxy, or halo; each Y isindependently an alkylene, aralkylene, or a combination thereof; each Gis independently a bond or a divalent residue equal to a diamine offormula R³HN-G-NHR³ minus the two —NHR³ groups; each R³ is independentlyhydrogen or alkyl or R³ taken together with G and with the nitrogen towhich they are both attached form a heterocyclic group; each n isindependently an integer of 0 to 300; each p is independently an integerof 1 to 25 and the average of p is 1.3 or greater; and each q isindependently an integer of 1 to 2, with an average of q is 1.05 orless.

Suitable examples of R¹, Y, G, and R³ are the same as described abovefor formula I.

The first step of the method of the disclosure comprises adding anoxalate ester of formula II to a solvent

wherein each R² is independently an alkyl, haloalkyl, aryl, or arylsubstituted with an alkyl, alkoxy, halo, alkyoxycarbonyl, or

bound through the N, wherein each R⁴ is independently hydrogen, alkyl,or aryl or R⁴ taken together form a ring.

The two R² groups in the oxalate of formula II can be the same ordifferent. In some methods, the two R² groups are different and havedifferent reactivity with the polydiorganosiloxane diamine of formulaIII below.

Suitable alkyl and haloalkyl groups for R² often have 1 to 10, 1 to 6,or 1 to 4 carbon atoms. Although tertiary alkyl (e.g., tert-butyl) andhaloalkyl groups can be used, there is often a primary or secondarycarbon atom attached directly (i.e., bonded) to the adjacent oxy group.Exemplary alkyl groups include methyl, ethyl, n-propyl, iso-propyl,n-butyl, and iso-butyl. Exemplary haloalkyl groups include chloroalkylgroups and fluoroalkyl groups in which some, but not all, of thehydrogen atoms on the corresponding alkyl group are replaced with haloatoms. For example, the chloroalkyl or a fluoroalkyl groups can bechloromethyl, 2-chloroethyl, 2,2,2-trichloroethyl, 3-chloropropyl,4-chlorobutyl, fluoromethyl, 2-fluoroethyl, 2,2,2-trifluoroethyl,3-fluoropropyl, 4-fluorobutyl, and the like. Suitable aryl groups for R²include those having 6 to 12 carbon atoms such as, for example, phenyl.An aryl group can be unsubstituted or substituted with an alkyl (e.g.,an alkyl having 1 to 4 carbon atoms such as methyl, ethyl, or n-propyl),an alkoxy (e.g., an alkoxy having 1 to 4 carbon atoms such as methoxy,ethoxy, or propoxy), halo (e.g., chloro, bromo, or fluoro), oralkoxycarbonyl (e.g., an alkoxycarbonyl having 2 to 5 carbon atoms suchas methoxycarbonyl, ethoxycarbonyl, or propoxycarbonyl).

The oxalates of formula II can be prepared, for example, by reaction ofan alcohol of formula R²—OH with oxalyl dichloride. Commerciallyavailable oxalates of formula II (e.g., from Sigma-Aldrich, Milwaukee,Wis. and from VWR International, Bristol, Conn.) include, but are notlimited to, dimethyl oxalate, diethyl oxalate, di-n-butyl oxalate,di-tert-butyl oxalate, bis(phenyl)oxalate, bis(pentafluorophenyl)oxalate, 1-(2,6-difluorophenyl)-2-(2,3,4,5,6-pentachlorophenyl) oxalate,and bis (2,4,6-trichlorophenyl) oxalate.

Particularly useful oxalate esters of formula II include, for example,oxalate esters of phenol, methyl ethyl ketone oxime, acetone oxime, andtrifluoroethanol; the latter oxalate esters being particularly preferredat present.

Suitable solvents include, for example, tetrahydrofuran, methyltert-butyl ether, toluene, ethyl acetate, dichloromethane, chloroformand the like, or any solvent that does not interfere with the desiredreaction.

As or after the oxalate ester is/has been added to the solvent,polydiorganosiloxane diamine of formula III is added and reacted withthe oxalate ester

The molar ratio of oxalate ester of formula II to polydiorganosiloxanediamine of formula III is commonly controlled to be at least about1:0.56. A molar ratio of at least 1:0.56 can, under typical observation,ensure that the oxalate ester of formula II is fully consumed in thereaction. As used herein, “fully consumed” and variations thereof meansno greater than 5% of the oxalate ester initially added to the solventremains available for reaction, as detected, for example, by gaschromatography. In other words, at least 95%, at least 96%, at least97%, at least 98%, at least 99%, or at least 99.5% of the oxalate esterinitially added to the solvent is converted during the reaction. Withoutwishing to be bound by theory, a full consumption of the oxalate esterof formula II aids in maintaining q in Formula I as close to 1 aspracticable by limiting the available bond sites for the creation of“runs” of hard segments (i.e., where q equals 2).

The polydiorganosiloxane diamine of formula III can be prepared by anyknown method and suitable molecular weight, such as a number averagemolecular weight in the range of 1,000 to 20,000 g/mole. In somepresently preferred embodiments, the polydiorganosiloxane diamine offormula III has a number average molecular weight of about 1,000 g/molto about 15,000 g/mol, and in other presently preferred embodiments thepolydiorganosiloxane diamine of formula III has a number averagemolecular weight of about 10,000 g/mol to about 15,000 g/mol. Thepresent inventors discovered that starting with a polydiorganosiloxanediamine of formula III having a number average molecular weight lessthan 20,000 g/mol allowed for a comparatively greater total number ofhard segments in the copolymers of the present disclosure as compared tostarting with a number average molecular weight of, for example, 25,000g/mol or greater. Without wishing to be bound by theory, an insufficientnumber of hard segments in the copolymer, as is typically the case whenstarting with a polydiorganosiloxane diamine of formula III having anumber average molecular weight of greater than about 23,000 g/mol,tends to reduce the shear holding strength and other performancecharacteristics of such adhesives. Moreover, the resulting compositionis difficult to coat on many desirable backings and other substrates.Suitable polydiorganosiloxane diamines and methods of making thepolydiorganosiloxane diamines are described, for example, in U.S. Pat.No. 3,890,269 (Martin), U.S. Pat. No. 4,661,577 (Jo Lane et al.), U.S.Pat. No. 5,026,890 (Webb et al.), U.S. Pat. No. 5,276,122 (Aoki et al.),U.S. Pat. No. 5,214,119 (Leir et al.), U.S. Pat. No. 5,461,134 (Leir etal.), U.S. Pat. No. 5,512,650 (Leir et al.), and U.S. Pat. No. 6,355,759(Sherman et al.). Some polydiorganosiloxane diamines are commerciallyavailable, for example, from Gelest Inc., Morrisville, Pa.

A polydiorganosiloxane diamine having a molecular weight greater than5,000 g/mole can be prepared using the methods described in U.S. Pat.No. 5,214,119 (Leir et al.), U.S. Pat. No. 5,461,134 (Leir et al.), andU.S. Pat. No. 5,512,650 (Leir et al.). One of the described methodsinvolves combining under reaction conditions and under an inertatmosphere (a) an amine functional end blocker of the following formula

where Y and R¹ are the same as defined for formula I′; (b) sufficientcyclic siloxane to react with the amine functional end blocker to form apolydiorganosiloxane diamine having a molecular weight less than 2,000g/mole; and (c) an anhydrous aminoalkyl silanolate catalyst of thefollowing formula

where Y and R¹ are the same as defined in formula I′ and M⁺ is a sodiumion, potassium ion, cesium ion, rubidium ion, or tetramethylammoniumion. The reaction is continued until substantially all of the aminefunctional end blocker is consumed and then additional cyclic siloxaneis added to increase the molecular weight. The additional cyclicsiloxane is often added slowly (e.g., drop wise). The reactiontemperature is often conducted in the range of 80° C. to 90° C. with areaction time of 5 to 7 hours. The resulting polydiorganosiloxanediamine can be of high purity (e.g., less than 2 weight percent, lessthan 1.5 weight percent, less than 1 weight percent, less than 0.5weight percent, less than 0.1 weight percent, less than 0.05 weightpercent, or less than 0.01 weight percent silanol impurities). Alteringthe ratio of the amine end functional blocker to the cyclic siloxane canbe used to vary the molecular weight of the resultingpolydiorganosiloxane diamine of formula III.

Another method of preparing the polydiorganosiloxane diamine of formulaIII includes combining under reaction conditions and under an inertenvironment (a) an amine functional end blocker of the following formula

where R¹ and Y are the same as described for formula I′ and where thesubscript x is equal to an integer of 1 to 150; (b) sufficient cyclicsiloxane to obtain a polydiorganosiloxane diamine having an averagemolecular weight greater than the average molecular weight of the aminefunctional end blocker; and (c) a catalyst selected from cesiumhydroxide, cesium silanolate, rubidium silanolate, cesiumpolysiloxanolate, rubidium polysiloxanolate, and mixtures thereof. Thereaction is continued until substantially all of the amine functionalend blocker is consumed. This method is further described in U.S. Pat.No. 6,355,759 B1 (Sherman et al.). This procedure can be used to prepareany molecular weight of the polydiorganosiloxane diamine.

Yet another method of preparing the polydiorganosiloxane diamine offormula III is described in U.S. Pat. No. 6,531,620 B2 (Brader et al.).In this method, a cyclic silazane is reacted with a siloxane materialhaving hydroxy end groups as shown in the following reaction.

The groups R¹ and Y are the same as described for formula I′. Thesubscript m is an integer greater than 1.

Examples of polydiorganosiloxane diamines include, but are not limitedto, polydimethylsiloxane diamine, polydiphenylsiloxane diamine,polytrifluoropropylmethylsiloxane diamine, polyphenylmethylsiloxanediamine, polydiethylsiloxane diamine, polydivinylsiloxane diamine,polyvinylmethylsiloxane diamine, poly(5-hexenyl)methylsiloxane diamine,and mixtures thereof.

The mixture of oxalate ester and polydiorganosiloxane diamine is allowedto react until essentially no polydiorganosiloxane diamine or oxalateester remains as measured, for example, by gas chromatography. Theresulting reaction product, precursor formula IV is formed

The resulting reaction mixture contains some ester-cappedpolydiorganosiloxane diamine in which p is dependent upon the amount ofoxalate ester utilized and on the nature of the solvent utilized. Thereaction mixture typically contains no more than trace (i.e., less than5% of the initial amount) unreacted oxalate ester of formula II asdetermined, for example, by gas chromatography.

Next, one or more diamines of formula V are added to the reactionproduct of formula IV to form the repeat unit of formula I′

The diamine is typically added in a quantity necessary to consume nearlyall if not all the remaining ester groups. This reaction is typicallyperformed in the presence of a catalyst, though the reaction can also bedone in the absence of a catalyst. Suitable catalysts include proticacid catalysts, such as acetic acid.

The molar ratio of polydiorganosiloxane diamine of formula III to thediamine(s) of formula V (i.e., the amine molar ratio) is often less thanor equal to about 1:0.8. The amine molar ratio is selected such that themolar ratio of total amine to ester in the copolymer of formula I′ isabout 1.0:1.0 (i.e., 0.96:1 to 1:1.04). For example, the amine molarratio can be in the range of 1:0.4 to 1:0.75, in the range of 1:0.45 to1:0.7, in the range of 1:0.5 to 1:0.65. Varying the amine molar ratiocan be used, for example, to alter the overall molecular weight and thenumber of hard segment “runs”, which can affect the rheology of theresulting copolymers. Additionally, varying the molar ratio can be usedto provide oxalylamino-containing end groups or amino end groups,depending upon which reactant is present in molar excess.

The diamines of formula V are sometimes classified as organic diamines.Organic diamines include, for example, those selected from alkylenediamines, heteroalkylene diamines, arylene diamines, aralkylenediamines, or alkylene-aralkylene diamines. The diamine has only twoamino groups so that the resulting polydiorganosiloxane polyoxamides andpolyoxamide-hydrazides are linear block copolymers that are oftenelastomeric, molten at elevated temperatures, and soluble in some commonorganic solvents. The diamine is free of a polyamine having more thantwo primary or secondary amino groups. Tertiary amines that do not reactwith the reaction product of formula IV can be present. Additionally,the diamine can be free of any carbonylamino groups in certainembodiments; that is, the diamine is not an amide.

Exemplary polyoxyalkylene diamines (i.e., G is a heteroalkylene with theheteroatom being oxygen) include, but are not limited to, thosecommercially available from Huntsman, The Woodlands, Tex. under thetrade designation JEFFAMINE D-230 (i.e., polyoxypropropylene diaminehaving an average molecular weight of 230 g/mole), JEFFAMINE D-400(i.e., polyoxypropylene diamine having an average molecular weight of400 g/mole), JEFFAMINE D-2000 (i.e., polyoxypropylene diamine having anaverage molecular weight of 2,000 g/mole), JEFFAMINE HK-511 (i.e.,polyetherdiamine with both oxyethylene and oxypropylene groups andhaving an average molecular weight of 220 g/mole), JEFFAMINE ED-2003(i.e., polypropylene oxide capped polyethylene glycol having an averagemolecular weight of 2,000 g/mole), and JEFFAMINE EDR-148 (i.e.,triethyleneglycol diamine).

Exemplary alkylene diamines (i.e., G is a alkylene) include, but are notlimited to, ethylene diamine, propylene diamine, butylene diamine,hexamethylene diamine, 2-methylpentamethylene 1,5-diamine (i.e.,commercially available from DuPont, Wilmington, Del. under the tradedesignation DYTEK A), 1,3-pentane diamine (commercially available fromDuPont under the trade designation DYTEK EP), 1,4-cyclohexane diamine,1,2-cyclohexane diamine (commercially available from DuPont under thetrade designation DHC-99), 4,4′-bis(aminocyclohexyl)methane, and3-aminomethyl-3,5,5-trimethylcyclohexylamine.

Exemplary arylene diamines (i.e., G is an arylene such as phenylene)include, but are not limited to, m-phenylene diamine, o-phenylenediamine, and p-phenylene diamine. Exemplary aralkylene diamines (i.e., Gis an aralkylene such as alkylene-phenyl) include, but are not limitedto 4-aminomethyl-phenylamine, 3-aminomethyl-phenylamine, and2-aminomethyl-phenylamine. Exemplary alkylene-aralkylene diamines (i.e.,G is an alkylene-aralkylene such as alkylene-phenylene-alkylene)include, but are not limited to, 4-aminomethyl-benzylamine,3-aminomethyl-benzylamine, and 2-aminomethyl-benzylamine.

Exemplary hydrazines (i.e., G is a bond) include, but are not limitedto, hydrazine and N,N′-diaminopiperazine.

In some preferred embodiments, the diamine of formula V is selected fromthe group consisting of 1,2-diaminoethane, 1,3-diaminopropane,1,4-diaminobutane, 1,5-diaminopentane, 2-methyl-1,5-pentanediamine,1,6-diaminohexane, and m-xylylenediamine.

Any suitable reactor (e.g., a glass vessel or a standard kettle equippedwith agitators) or process can be used to prepare the copolymericmaterial according to the method of the disclosure. The reaction can beconducted using a batch process, semi-batch process, or a continuousprocess. Exemplary batch processes can be conducted in a reaction vesselequipped with a mechanical stirrer such as a Brabender mixer, providedthe product of the reaction is in a molten state has a sufficiently lowviscosity to be drained from the reactor. Exemplary semi-batch processcan be conducted in a continuously stirred tube, tank, or fluidized bed.Exemplary continuous processes can be conducted in a single screw ortwin screw extruder such as a wiped surface counter-rotating orco-rotating twin screw extruder.

The silicone polyoxamide and silicone polyoxamide-hydrazide copolymersof the disclosure are linear block copolymers (i.e., they comprise hardblocks and soft blocks) and can be elastomeric. The silicone polyoxamideand silicone polyoxamide-hydrazide copolymers can be formulated toinclude at least 93 weight percent polydiorganosiloxane segments (i.e.,soft segments) based on the weight of the copolymer. In otherembodiments, the silicone polyoxamide copolymers can be formulated toinclude at least 94 wt. %, at least 95 wt. % at least 96 wt. %, at least97 wt. %, at least 98 wt. %, at least 99 wt. %, or at least 99.2 wt. %polydiorganosiloxane segments (i.e., soft segments) based on the weightof the copolymer. The weight percent of the diorganosiloxane in thepolydiorganosiloxane segments can be controlled by using relativelylower molecular weight polydiorganosiloxanes of formula III.

The copolymers of the disclosure also tend to have improved heatstability. Some of the copolymers of the disclosure, for example, do notflow at or below about 220° C., at or below about 260° C., or even at orbelow about 300° C. For the purposes of this disclosure, the temperatureat which a copolymer flows is defined as the temperature at which thecopolymer is sufficiently soft such that it compresses to a thickness of2 mm in an ARES parallel plate rheometer (available from TA Instruments,New Castle, Del.).

The copolymers of the disclosure can be optically clear. As used herein,the term “optically clear” refers to a material that is clear to thehuman eye. An optically clear copolymeric material often has a luminoustransmission of at least 90 percent, a haze of less than 2 percent, andopacity of less than 1 percent in the 400 to 700 nm wavelength range.Both the luminous transmission and the haze can be determined using, forexample, the method of ASTM-D 1003-95.

Additionally, the copolymers can have a low refractive index. As usedherein, the term “refractive index” refers to the absolute refractiveindex of a material (e.g., copolymeric material) and is the ratio of thespeed of electromagnetic radiation in free space to the speed of theelectromagnetic radiation in the material of interest. Theelectromagnetic radiation is white light. The index of refraction ismeasured using an Abbe refractometer, available commercially, forexample, from Fisher Instruments of Pittsburgh, Pa. The measurement ofthe refractive index can depend, to some extent, on the particularrefractometer used. The copolymeric material usually has a refractiveindex in the range of 1.41 to 1.50.

The copolymers of the present disclosure can be cast from solvents orcast and polymerized as film, molded or embossed in various shapes, orextruded into films. The high temperature stability of the copolymericmaterial makes them well suited for extrusion methods of film formation.The films can be optically clear. A multilayer film containingpolydiorganosiloxane polyoxamide block copolymers is described, forexample, in U.S. Pat. No. 7,820,297 (Benson et al.).

The copolymers of the disclosure are useful in various articles. Thearticles, for example, can include a layer containing the copolymer ofthe disclosure and one or more optional substrates. For example, thecopolymer of the disclosure can be in a layer adjacent to a firstsubstrate or positioned between a first substrate and a secondsubstrate. That is, the article can be arranged in the following order:a first substrate, a layer containing the copolymer of the disclosure,and a second substrate. As used herein, the term “adjacent” refers to afirst layer that contacts a second layer or that is positioned inproximity to the second layer but separated from the second layer by oneor more additional layers.

The copolymers of the disclosure are also useful as low adhesionbacksize coatings.

Adhesive Compositions featuring Silicone Polyoxamide Copolymers

The silicone polyoxamide copolymers of the disclosure can be formulatedinto adhesive compositions such as pressure sensitive adhesives and heatactivated adhesives that contain a tackifier. Such adhesive compositionsare further described, for example, in U.S. Pat. No. 7,371,464 (Shermanet al.) and U.S. Pat. No. 8,691,391 (Sherman et al). The copolymers ofthe disclosure can be formulated into both stretch release and peelrelease compositions. In embodiments featuring a stretch releasableadhesive, the article can be removed from a substrate or surface bystretching it at an angle of less than 35°. In embodiments featuring apeel-releasable (i.e., peelable) adhesive, the article is a single ormultilayer construction that can be removed from a substrate or surfacesby stretching it an angle of 35° or greater. In some embodiments, thereleasable adhesive may be removed by a combination of stretch andpeel-release mechanisms.

Additionally, the copolymers of the disclosure can be used as a hot meltadhesive. Typically, the hot melt adhesive contains little or notackifier. The hot melt adhesives can be used, for example, to bond twosurfaces together into a composite. That is, the hot melt adhesive canbe used to bond a first substrate to a second substrate with the hotmelt adhesive positioned between the first and second substrates. Duringapplication to a surface such as the surface of a substrate, hot meltadhesives are desirably sufficiently fluid to wet the surface completelyand leave no voids, even if the surface is rough. Such an adhesivecomposition typically has a low viscosity at the time of application andthen sets into a solid upon cooling. The cohesive strength develops uponcooling. Alternatively, the hot melt adhesive composition can beformulated with a solvent or carrier that lowers the viscositysufficiently to permit wetting of the surface. The solvent or carriercan then be removed to provide a solid coating having cohesive strength.

Tackifiers, plasticizers, and other property modifiers may be formulatedinto adhesive compositions including the copolymers of the disclosure.Preferred optional additives are not hot melt processable. That is, theydo not melt and flow at the temperatures at which the copolymer of thedisclosure melts and flows.

Tackifying materials or plasticizers useful with the polymeric materialsare preferably miscible at the molecular level, e.g., soluble in, any orall of the polymeric segments of the elastomeric material or thethermoplastic elastomeric material. Examples of tackifiers suitable forthe disclosure include but are not limited to silicone fluids, liquidrubbers, hydrocarbon resins, rosin, natural resins such as dimerized orhydrogenated balsams and esterified abietic acids, polyterpenes, terpenephenolics, phenol-formaldehyde resins, and rosin esters. Examples ofplasticizers include but are not limited to polybutene, paraffinic oils,petrolatum, and certain phthalates with long aliphatic side chains suchas ditridecyl phthalate.

Other suitable tackifiers include silicate tackifying resins. Suitablesilicate tackifying resins include those resins composed of thefollowing structural units M (i.e., monovalent R₃SiO_(1/2) units), D(i.e., divalent R₂SiO_(2/2) units), T (i.e., trivalent RSiO_(3/2)units), and Q (i.e., quaternary SiO_(4/2) units), and combinationsthereof. Typical exemplary silicate resins include MQ silicatetackifying resins, MQD silicate tackifying resins, and MQT silicatetackifying resins. These silicate tackifying resins usually have anumber average molecular weight in the range of 100 to 50,000 or in therange of 500 to 15,000 and generally have methyl R groups.

MQ silicate tackifying resins are copolymeric resins having R₃SiO_(1/2)units (“M” units) and SiO_(4/2) units (“Q” units), where the M units arebonded to the Q units, each of which is bonded to at least one other Qunit. Some of the SiO_(4/2) units (“Q” units) are bonded to hydroxylradicals resulting in HOSiO_(3/2) units (“TOH” units), therebyaccounting for the silicon-bonded hydroxyl content of the silicatetackifying resin, and some are bonded only to other SiO_(4/2) units.

Such resins are described in, for example, Encyclopedia of PolymerScience and Engineering, vol. 15, John Wiley & Sons, New York, (1989),pp. 265-270, and U.S. Pat. No. 2,676,182 (Daudt et al.), U.S. Pat. No.3,627,851 (Brady), U.S. Pat. No. 3,772,247 (Flannigan), and U.S. Pat.No. 5,248,739 (Schmidt et al.). Other examples are disclosed in U.S.Pat. No. 5,082,706 (Tangney). The above-described resins are generallyprepared in solvent. Dried or solventless, M silicone tackifying resinscan be prepared, as described in U.S. Pat. No. 5,319,040 (Wengrovius etal.), U.S. Pat. No. 5,302,685 (Tsumura et al.), and U.S. Pat. No.4,935,484 (Wolfgruber et al.).

Certain MQ silicate tackifying resins can be prepared by the silicahydrosol capping process described in U.S. Pat. No. 2,676,182 (Daudt etal.) as modified according to U.S. Pat. No. 3,627,851 (Brady), and U.S.Pat. No. 3,772,247 (Flannigan). These modified processes often includelimiting the concentration of the sodium silicate solution, and/or thesilicon-to-sodium ratio in the sodium silicate, and/or the time beforecapping the neutralized sodium silicate solution to generally lowervalues than those disclosed by Daudt et al. The neutralized silicahydrosol is often stabilized with an alcohol, such as 2-propanol, andcapped with R₃SiO_(1/2) siloxane units as soon as possible after beingneutralized. The level of silicon bonded hydroxyl groups (i.e., silanol)on the MQ resin may be reduced to no greater than 1.5 weight percent, nogreater than 1.2 weight percent, no greater than 1.0 weight percent, orno greater than 0.8 weight percent based on the weight of the silicatetackifying resin. This may be accomplished, for example, by reactinghexamethyldisilazane with the silicate tackifying resin. Such a reactionmay be catalyzed, for example, with trifluoroacetic acid. Alternatively,trimethylchlorosilane or trimethylsilylacetamide may be reacted with thesilicate tackifying resin, a catalyst not being necessary in this case.

MQD silicone tackifying resins are terpolymers having R₃SiO_(1/2) units(“M” units), SiO_(4/2) units (“Q” units), and R₂SiO_(2/2) units (“D”units) such as are taught in U.S. Pat. No. 2,736,721 (Dexter). In MQDsilicone tackifying resins, some of the methyl R groups of theR₂SiO_(2/2) units (“D” units) can be replaced with vinyl (CH₂═CH—)groups (“DVi” units).

MQT silicate tackifying resins are terpolymers having R₃SiO_(1/2) units,SiO_(4/2) units and RSiO_(3/2) units (“T” units) such as are taught inU.S. Pat. No. 5,110,890 (Butler) and Japanese Kokai HE 2-36234.

Suitable silicate tackifying resins are commercially available fromsources such as Dow Corning, Midland, Mich.; Momentive PerformanceMaterials, Albany, N.Y.; and Rhodia Silicones, Rock Hill, S.C. Examplesof particularly useful MQ silicate tackifying resins include thoseavailable under the trade designations SR-545 and SR-1000, both of whichare commercially available from Momentive Performance Materials, Albany,N.Y. Such resins are generally supplied in organic solvent and may beemployed in the formulations of the adhesives of the present disclosureas received. Blends of two or more silicate resins can be included inthe adhesive compositions.

Either pressure sensitive adhesives or heat activated adhesives can beformulated by combining the silicone polyoxamide and/or siliconepolyoxamide-hydrazide copolymers and a silicate tackifying resin withinorganic particles or other filler. The inorganic particles included inthe adhesive composition tend to enhance the performance of theresulting adhesive. More particularly, the inorganic particles tend toincrease the cohesive strength of the pressure-sensitive adhesive andtend to increase the rubbery plateau modulus. The inorganic particlescan be uniformly or non-uniformly distributed throughout thepressure-sensitive adhesive composition. The inorganic particles can beany suitable metal, metal alloy, metal oxide, ceramic material, ormixture thereof. The inorganic particles are often selected from, butnot limited to, alumina, titania, zirconia, silica, or the like.

In many embodiments, the inorganic particles are fumed silica particles.Suitable fumed silica is commercially available, for example, under thetrade designation AEROSIL (e.g., AEROSIL R972, R974, R976, R300, R380,R130, R150, R200, R202, R805, and R812) from Evonik Industries (Essen,Germany) or under the trade designation CABOSIL (e.g., CABOSIL TS-720,TS-610, TS-530, and TS-500) from Cabot (Alpharetta, Ga.). The fumedsilica can have any suitable surface area. For example, the surface areacan be in the range of 1 to 500 m²/gram, in the range of 10 to 400m²/gram, or in the range of 100 to 400 m²/gram. The fumed silica canhave any suitable particle size. In some applications, the fumed silicahas an average primary particle size less than 30 microns, less than 15microns, less than 10 microns, less than 5 microns, and less than 1micron. While nanoscale fumed silica may be used in certainimplementations, the use of fumed silica having an average primaryparticle size less than 200 nanometers may result in substrate damage.Although either hydrophobic or hydrophilic fumed silica can be used,hydrophobic fumed silica is often used because such particles tend todisperse better in the organic solvents typically included in thevarious compositions.

In other embodiments, the inorganic particles are aerogels such assilica aerogel particles (e.g., crushed aerogels or aerogel powder). Thesilica aerogel particles often have pores in the nanometer range (e.g.,less than 100 nanometers or less than 50 nanometers) and have surfaceareas equal to at least 500 m²/gram. Exemplary aerogel silica particlescan have an average particle size that is less than 20 microns or lessthan 10 microns. Although the size of the silica aerogel particles islarger than the wavelength of light, the particles are often translucentand can be used to form adhesive layers that are relatively clear eventhough they may not be considered to be optically clear. Exemplarysilica aerogel particles in translucent and opacified grades arecommercially available under the trade designation NANOGEL from Cabot(Billerica, Mass.).

Although the inorganic particles can be surface modified to facilitatedispersion in the silicone polymer or the adhesive composition, theinorganic particles are often not surface modified. The inorganicparticles can be agglomerated or non-agglomerated and aggregated ornon-aggregated. The inorganic particles can have any desired particlesize or particle shape. If an optically clear adhesive article isdesired, the inorganic particles are often selected to have an averageparticle size that is less than 1000 nanometers. For example, theaverage particle size is often less than 500 nanometers, less than 200nanometers, less than 100 nanometers, or less than 50 nanometers. Toprepare adhesive articles that do not need to be optically clear, largerinorganic particles can be used. For example, the inorganic particlescan have an average particle size up to 5 micrometers, up to 10micrometers, up to 20 micrometers, up to 50 micrometers, or up to 100micrometers.

The adhesive compositions can further optionally include other additivesto provide desired properties. For example, dyes and pigments can beadded as colorant; electrically and/or thermally conductive compoundscan be added to make the adhesive electrically and/or thermallyconductive or antistatic; antioxidants and antimicrobial agents can beadded; and ultraviolet light stabilizers and absorbers, such as hinderedamine light stabilizers (HALS), can be added to stabilize the adhesiveagainst ultraviolet degradation and to block certain ultravioletwavelengths from passing through the article. Other additives include,but are not limited to, adhesion promoters, additional fillers (e.g.,carbon fibers, carbon black, glass beads, glass and ceramic bubbles,glass fibers, mineral fibers, clay particles, organic fibers such asnylon, metal particles, or unexpanded polymeric microspheres), tackenhancers, blowing agents, hydrocarbon plasticizers, andflame-retardants.

The copolymers of the present disclosure are typically present inadhesive compositions in quantities of at least 20 wt. % and no greaterthan 80 wt. %, based on the total weight of the adhesive composition, orany amount within that range. In certain implementations, it may bepreferred that the copolymer is present at a concentration of at least30 wt. % and no greater than 75 wt. %, based on the total weight of theadhesive composition.

The tackifier is typically added to the composition to at least 10 wt.%, in some embodiments at least 30 wt. %, in some embodiments at least40 wt. %, in some embodiments at least 50 wt. %, based on the totalweight of the adhesive composition. The tackifier is typically presentin composition at no greater than 70 wt. %, no greater than 65 wt. %,and in some embodiments no greater than 60 wt. % based on the totalweight of the adhesive composition. In typical adhesive compositionsused for mounting applications herein, the tackifier is present in thecomposition at no greater than about 60 wt. % and no less than 40 wt. %.Without wishing to be bound by theory, a level of tackifier above about60 wt. % can, in certain conditions, mean the tackifier assumes thecontinuous phase of the composition in favor of the copolymer. Adhesivecompositions with a tackifier forming the continuous phase tend toexhibit at least one of poor tack, poor adhesion poor shear holdingstrength, and insufficiently damage-free removal.

Typically, the inorganic particles, if used as filler, will be added toa level of about 0.10% to about 20% by weight based upon the totalweight of the adhesive composition, or any amount within that range. Inpresently preferred implementations the inorganic particles are added toa level of about 3% to about 15% by weight, and more preferably 5% to12% by weight based upon the total weight of the adhesive composition.

Adhesive Articles

An adhesive article typically includes a substrate and an adhesive layeradjacent to at least one surface of the substrate. Other adhesivearticles of the present disclosure may be backing or substrate free.Backing free adhesive constructions are described, for example, in USPublication No. 2016/0068722 (Schmitz-Stapela et al.). The adhesivelayer includes the adhesive compositions including the copolymersdescribed herein. The substrates can include a single layer of materialor can be a combination of two or more materials.

The substrates can have any useful form including, but not limited to,films, sheets, membranes, filters, nonwoven or woven fibers, hollow orsolid beads, bottles, plates, tubes, rods, pipes, or wafers. Thesubstrates can be porous or non-porous, rigid or flexible, transparentor opaque, clear or colored, and reflective or non-reflective. Thesubstrates can have a flat or relatively flat surface or can have atexture such as wells, indentations, channels, bumps, or the like. Thesubstrates can have a single layer or multiple layers of material.Suitable substrate materials include, for example, polymeric materials,glasses, ceramics, sapphire, metals, metal oxides, hydrated metaloxides, or combinations thereof.

Suitable polymeric substrate materials include, but are not limited to,polyolefins (e.g., polyethylene such as biaxially oriented polyethyleneor high density polyethylene and polypropylene such as biaxiallyoriented polypropylene), polystyrenes, polyacrylates, polymethacrylates,polyacrylonitriles, polyvinyl acetates, polyvinyl alcohols, polyvinylchlorides, polyoxymethylenes, polyesters such as polyethyleneterephthalate (PET), polytetrafluoroethylene, ethylene-vinyl acetatecopolymers, polycarbonates, polyamides, rayon, polyimides,polyurethanes, phenolics, polyamines, amino-epoxy resins, polyesters,silicones, cellulose based polymers, polysaccharides, nylon, neoprenerubber, or combinations thereof. Some polymeric materials are foams,woven fibers, non-woven fibers, or films.

Suitable glass and ceramic substrate materials can include, for example,silicon, aluminum, lead, boron, phosphorous, zirconium, magnesium,calcium, arsenic, gallium, titanium, copper, or combinations thereof.Glasses typically include various types of silicate containingmaterials.

Some substrates are release liners. The adhesive layer can be applied toa release liner and then transferred to another substrate such as abacking film or foam substrate. Suitable release liners typicallycontain a polymer such as polyester or polyolefin or a coated paper.Some adhesive articles transfer tape that contains an adhesive layerpositioned between two release liners. Exemplary release liners include,but are not limited to, polyethylene terephthalate coated with afluorosilicone such as that disclosed in U.S. Pat. No. 5,082,706(Tangney) and commercially available from Loparex, Inc., Bedford Park,Ill. The liner can have a microstructure on its surface that is impartedto the adhesive to form a microstructure on the surface of the adhesivelayer. The liner can be removed to provide an adhesive layer having amicrostructured surface.

In some embodiments, the adhesive article is a single sided adhesivetape in which the adhesive layer is on a single major surface of asubstrate such as a foam or film. In other embodiments, the adhesivearticle is a double-sided adhesive tape in which the adhesive layer ison two major surfaces of a substrate such as a foam or film. The twoadhesive layers of the double-sided adhesive tape can be the same ordifferent. For example, one adhesive can be a pressure sensitiveadhesive and the other a heat activated adhesive where at least one ofthe adhesives is based on the copolymer described herein. Each exposedadhesive layer can be applied to another substrate.

The adhesive articles can contain additional layers such as primers,barrier coatings, metal and/or reflective layers, tie layers, andcombinations thereof. The additional layers can be positioned betweenthe substrate and the adhesive layer, adjacent the substrate oppositethe adhesive layer, or adjacent to the adhesive layer opposite thesubstrate.

In some embodiments, the adhesive articles can further include aseparable connector. Some exemplary separable connectors are describedin, for example, U.S. Pat. Nos. 6,572,945; 7,781,056; 6,403,206; and6,972,141.

Some adhesive articles of the present disclosure have excellent shearstrength. Some embodiments of the present disclosure have a shearstrength of greater than 1800 minutes as measured according to ASTMD3654-82, as modified according to the Static Shear Test Method below.Some embodiments of the present disclosure have shear strength ofgreater than 10,000 minutes as measured according to modified ASTMD3654-82. Some embodiments of the present disclosure have shear strengthof greater than 50,000 minutes as measured according to modified ASTMD3654-82.

Some adhesives that can be used in the adhesive articles of the presentdisclosure have a glass transition temperature of about −125° C. to 15°C., as determined by dynamic mechanical analysis of the tan δ peakvalue. Some adhesives that can be used in the adhesive articles of thepresent disclosure have a storage modulus of about 400,000 Pa or less,or 300,000 or less at 25° C., as determined by dynamic mechanicalanalysis.

In some embodiments, the thickness of the adhesive on at least one ofthe first or second major surfaces of the multilayer carrier is about 1μm to about 1 mm.

Some adhesive articles of the present disclosure have an elongation atbreak of greater than 50% in at least one direction. Some adhesivearticles of the present disclosure have an elongation at break ofbetween about 50% and about 1200% in at least one direction.

Some adhesive articles of the present disclosure have a tensile strengthat break sufficiently high so that the adhesive article will not ruptureprior to being removed from an adherend at an angle of 35° or less.

Some adhesive articles of the present disclosure have a lower peel forceto make the adhesive article easier to remove (e.g., a force betweenabout 25 oz/in to about 50 oz/in). Some adhesive articles of the presentdisclosure can have a higher peel force as to permit handling of theadhesive article by the user without accidental separation (e.g., aforce between about 50 oz/in to 100 oz/in). Some embodiments of thepresent disclosure have a peel force between about 20 oz/in to 90 oz/in.Some embodiments of the present disclosure have a peel force betweenabout 30 oz/in to 70 oz/in.

Some adhesive articles of the present disclosure have a tensile strengthat break sufficiently high so that the adhesive article will not ruptureprior to being removed from an adherend at an angle of 35° or greater.

Some adhesive articles of the present disclosure can be removed from asubstrate, wall, or surface (generally, an adherend) without damage. Asused herein, the terms “without damage” and “damage-free” or the likemeans the adhesive article can be separated from the substrate withoutcausing visible damage to paints, coatings, resins, coverings, or theunderlying substrate and/or leaving behind residue. Visible damage tothe substrates can be in the form of, for example, scratching, tearing,delaminating, breaking, crumbling, straining, blistering, bubbling, andthe like to any layers of the substrate. Visible damage can also bediscoloration, weakening, changes in gloss, changes in haze, or otherchanges in appearance of the substrate.

A method of making an adhesive article typically includes providing asubstrate and applying an adhesive composition to at least one surfaceof the substrate. The adhesive composition can be applied to thesubstrate by a wide range of processes such as, for example, solutioncoating, solution spraying, hot melt coating, extrusion, coextrusion,lamination, and pattern coating. The adhesive composition is oftenapplied as an adhesive layer to a surface of substrate with a coatingweight of 0.02 grams/154.8 cm² to 2.4 grams/154.8 cm².

The adhesive articles of the disclosure may be exposed to postprocessing steps such as curing, crosslinking, die cutting, heating tocause expansion of the article, e.g., foam-in-place, and the like.

The adhesive articles featuring adhesive compositions of the presentdisclosure can be used in various ways. In some embodiments, theadhesive article is applied, attached to, or pressed into an adherend.In this way, the adhesive article contacts the adherend. Where a releaseliner is present, the release liner is removed before the adhesivearticle is applied, attached to, or pressed into an adherend. In someembodiments, at least a portion of the adherend is wiped with alcoholbefore the adhesive article is applied, attached to, or pressed into anadherend.

The adhesive articles may be used in wet or high humidity environmentssuch as those found in bathrooms. For example, they can be adhered totoilets (e.g., toilet tanks), bathtubs, sinks, and walls. The adhesivearticle may be used in showers, locker rooms, steam rooms, pools, hottubs, and kitchens (e.g., kitchen sinks, dishwashers and back splashareas, refrigerators and coolers). The adhesive article may also be usedin low temperatures applications including outdoor applications andrefrigerators. Useful outdoor applications include bonding articles suchas signage to outdoor surfaces such as windows, doors and vehicles.

The adhesive article (i.e., those in adhesive tapes or single article)can be provided in any useful form including, e.g., tape, strip, sheet(e.g., perforated sheet), label, roll, web, disc, and kit (e.g., anobject for mounting and the adhesive tape used to mount the object).Likewise, multiple adhesive articles can be provided in any suitableform including, e.g., tape, strip, sheet (e.g., perforated sheet),label, roll, web, disc, kit, stack, tablet, and combinations thereof inany suitable package including, for example, dispenser, bag, box, andcarton.

To remove the adhesive article from the adherend, at least a portion ofthe adhesive article is peeled or stretched away from the adherend. Insome embodiments, the angle of stretch is 350 or less. In embodimentswhere a tab is present, the user can grip the tab and use it to releaseor remove the adhesive article from the adherend.

The adhesive articles may be used to mount various items and objects tosurfaces such as painted drywall, plaster, concrete, glass, ceramic,fiberglass, metal or plastic. Items that can be mounted include, but arenot limited to, wall hangings, organizers, holders, baskets, containers,anti-slip mats, decorations (e.g., holiday decorations), calendars,posters, dispensers, wire clips, body side molding on vehicles, carryinghandles, signage applications such as road signs, vehicle markings,transportation markings, and reflective sheeting.

The adhesive articles may be used to mount items and materials, such asanti-slip mats or anti-fatigue mats, to a floor surface or the bottom ofa tub or shower, or to secure items, such as area rugs, to a floor. Theadhesive article can be used in various joining and assemblingapplications including such as adhering at least two containers (e.g.,boxes) for later separation. The adhesive article can be used in variouscushioning and sound deadening applications such as, for example,cushioning materials for placement beneath objects, sound insulatingsheet materials, vibration dampening, and combinations thereof. Theadhesive article can be used in various closure applications includingcontainer closures (e.g., box closures, closures for food containers,and closures for beverage containers), diaper closures, and surgicaldrape closures. The adhesive article can be used in various thermalinsulation applications. The adhesive article can be used in varioussealing applications such as in gaskets for liquids, vapors (e.g.,moisture), and dust. The adhesive article can be used in various labelssuch as removable labels (e.g., notes, price tags, and identificationlabels on containers), and in signage. The adhesive article can be usedin various medical applications (e.g., bandages, wound care, and medicaldevice labeling such as in a hospital setting). The adhesive article canbe used in various fastening applications such as fastening one object(e.g., a vase or other fragile object) to another object (e.g., a tableor a book shelf). The adhesive article can be used in various securingapplications such as fastening one or more components of a lockingmechanism to a substrate (e.g., a child safety lock can be adhered to acabinet or cupboard). The adhesive article can be used in various tamperindicating applications (e.g., tamper indicating articles). The adhesivearticle can also be incorporated in a variety of other constructionsincluding, but not limited to, abrasive articles (e.g., for sanding),articles for sanding and polishing applications (e.g., buffing pads,disc pads, hand pads, and polishing pads), pavement marking articles,carpeting (e.g., backing for carpeting), and electronic devices (e.g.,securing a battery within a housing in a cell phone or PDA (personaldigital assistant) to prevent unwanted movement).

The foregoing describes the disclosure in terms of embodiments foreseenby the inventor for which an enabling description was available,notwithstanding that insubstantial modifications of the disclosure, notpresently foreseen, may nonetheless represent equivalents thereto.

EXAMPLES

These examples are merely for illustrative purposes only and are notmeant to be limiting on the scope of the appended claims. Unlessotherwise noted or readily apparent from the context, all parts,percentages, ratios, etc. in the Examples and the rest of thespecification are by weight.

Materials

Solvents were obtained from EMD Chemicals, Gibbstown, N.J. unlessotherwise noted.

Abbreviation Description and Source PDMS diamine A polydimethylsiloxanediamine of the following formula

with a number average molecular weight of between approximately 10,000g/mole (5 k) and 15,000 g/mole (15 k) prepared according to U.S. Pat.No. 5,214,119. BTFEO Bis(2,2,2-trifluoroethyl)oxalate was preparedaccording to U.S. Pat. No. 8,765,881. EtOAc Ethyl acetate was obtainedfrom Honeywell (Morrisville, NJ) and dried over 4Å molecular sievesprior to use. AcOH Acetic acid obtained from Alfa Aesar (Ward Hill, MA).EDA Ethylene diamine obtained from Alfa Aesar (Ward Hill, MA). MQ resinMomentive SR545, Momentive Performance Materials LLC (Waterford, NY) IPAIsopropanol obtained from VWR International LLC (Radnor, PA)

Test Methods Titration Method to Determine Amine Equivalent Weight (AEW)of PDMS Diamines

The amine equivalent weights (AEW) of PDMS diamines were determined intetrahydrofuran (THF) using standardized HCl (0.1N) and titratingagainst a bromophenol blue endpoint.

Inherent Viscosity (IV)

Inherent viscosity measurements were performed at 27° C. on a LAUDA PVS1 viscosity system obtained from Lauda-Brinkman (Delran, N.J.) utilizingsize 50 capillary viscometers (Part #9721-A00) or from Cannon InstrumentCompany (State College, Pa.) or on an automated mini PV-HX Single-BathDilute Solution Polymer Viscometer with size OB viscometer tube (Part#12.0548) obtained from Cannon Instrument Company (State College, Pa.).All polymer samples were analyzed as an EtOAc solution at aconcentration of 0.2 grams/deciliter and IV measurements are reported inunits of deciliters/gram (dL/g).

Gas Chromatography (GC)

Gas chromatographic analysis was performed on an HP-6890 seriesinstrument using an HP-1 column (30 m×0.250 mm, 1.0 micron) obtainedfrom Agilent (Santa Clara, Calif.). Samples were injected undiluted as a30 wt % polymer solution in ethyl acetate.

Test Adherends

Drywall panels (obtained from Materials Company, Metzger Building, St.Paul, Minn.) were painted with Behr PREMIUM PLUS ULTRA® Primer and Paint2 in 1 Flat Egyptian Nile (FEN) (obtained from Behr Process Corporation,Santa Ana, Calif.), Sherwin-Williams DURATION®, Interior Acrylic LatexBen Bone White Paint (BB) (obtained from Sherwin-Williams Company,Cleveland, Ohio) or Valspar Reserve Superior Blue with Satin Sheen (BO)(bought from Lowes).

Procedure for painting: a first coat of paint was applied to a panelusing a paint roller, followed by air drying for 24 hours at ambientconditions. A second coat of paint was applied and dried at ambientconditions for 24 hours. The panel was placed in a forced air oven setto 50° C. for 7 days. Then the panel was then stored at ambientconditions until use.

Panels of glass and painted drywall measuring 2 in×2 in (5.1 cm×5.1 cm)were used for Shear Strength testing. Panels of glass and painteddrywall measuring 6 in×12 in (15.2 cm×30.5 cm) were used for PeelAdhesion and Package Weight Claim testing at 72° F./75 RH %.

Static Shear Test Method

Static shear was determined according to the method of ASTM D3654-82entitled, “Holding Power of Pressure-Sensitive Tapes,” with thefollowing modifications. The release liner(s), where present, wasremoved from the test sample. Test samples having the dimensions 0.5in×0.5 in (1.91 cm×1.91 cm) were adhered to the test substrate throughthe adhesive composition at 72° F. (22° C.) and 50% relative humidity(CTH) by passing a 15 lb. (6.8 kg) hand held roller over the length ofthe sample two times at a rate of 12 in/min (30.48 cm/min). A metalvapor coated polyester film having the dimensions 0.75 in×4 in (1.91cm×10.16 cm) was bonded to one side of the adhesive test sample for thepurpose of attaching the load.

The test sample was allowed to dwell on the test substrate for 1 hour at22° C. and 50% relative humidity; thereafter a 2.2 lb. (1 kg) weight wasapplied to the metal vapor coated polyester film. In case of highhumidity experiments, the samples were dwelled on the test substrate for1 hour at 90° F./90% RH (32.2 C/90% RH) in a Thermotron humidity chamberand tested in the same environment for the duration of test. The time tofailure was recorded in minutes and the average value, calculatedpursuant to procedures A and C of section 10.1 of the standard, for allof the test samples was reported. Three samples were tested and theaverage time to failure of the three samples and the failure mode ofeach sample was recorded. A value was reported with a greater thansymbol (i.e., >) when at least one of the three samples had not failedat the time the test was terminated.

Package Weight Claim Test (PWC)

Multi-layer composite tape samples were used to fulfill the packageweight claim test. The test was performed using medium size COMMANDutility hooks (Type 17001ES, available from 3M Company, St. Paul,Minn.). Test samples were cut into ⅝ in×2 in (1.6 cm×5.1 cm) strips. Thefirst adhesive side of the test sample was first applied to thesubstrate (i.e., Painted drywall, Tile or glass) by hand and thenadhered to the substrate by passing a 15 lb. (6.8 kg) hand held rollerover the length of the sample two times at a rate of 12 in/min (30.48cm/min). In the next step, the backplate or mounting base of the COMMANDutility hook was applied to the opposing first adhesive side of the testsample. Finally, the hook was attached to the backplate. The sampleswere mounted in a vertical position and allowed to dwell on the testsubstrate for 60 minutes at ambient conditions (between 69-72° F.(21-22° C.) and 10-40% relative humidity, depending on the time of year)before attaching a load to the test sample (31b weights). Samples werehung until failure or until 30 days had elapsed. Failure was indicatedwhen it was observed that hook article completely fell off the testsubstrate (the adhesive no longer adhered to the test substratesurface). The Package Weight Claim data in the Tables is provided asWeight Holding Power (days). The data are an average of 3 tests.

Some package weight testing was performed with medium size COMMANDUtility hook (strip size: ⅝″×2″, available from 3M Company) on FEN, BBor BO painted drywalls in 72° F./75% RH condition.

Some package weight testing was also carried out in a shower spraychamber at 95% RH using a continuous H₂O spray with a water temperatureof 105° F.-120° F. (41° C.-49° C.). Medium size COMMAND Utility hook(strip size: ⅝″×2″, available from 3M Company) were used in this test.Samples were adhered to White Glazed Ceramic Wall Tile (Interceramic,Carollton, Tex.), and the load on the samples was 3 lbs.

Liner Peel Release Test

Samples were tested at CTH conditions.

Easy Side:

A 2.54 cm wide and approximately 20 cm long sample of the adhesivetransfer tape on liner was cut using a specimen razor cutter. At least 4transfer adhesive tapes prepared as described below were laid down ontop of each other such that the adhesive side on each strip was broughtin contact with the liner side of the next strip. The stack of at leasttwo strips was applied lengthwise onto the platen surface of a peeladhesion tester (an IMASS SP-2100 tester, obtained from IMASS, Inc.,Accord, Mass.) using 3M Double Coated Paper Tape 410M (available from 3MCompany, St. Paul, Minn., USA). The top strip was peeled from the linerunderneath at an angle of 180 degrees at, e.g., 60 in/min (152.4cm/min). The average force required to peel three strips from theirunderneath counterparts was recorded as the easy side liner release (asgrams per inch).

Tight Side:

A 2.54 cm wide and approximately 20 cm long sample of the adhesivetransfer tape on liner was cut using a specimen razor cutter. The cutsample was applied lengthwise onto the platen surface of a peel adhesiontester (an IMASS SP-2100 tester, obtained from IMASS, Inc., Accord,Mass.) using 3M Double Coated Paper Tape 410M (available from 3MCompany, St. Paul, Minn., USA). The release liner was peeled from theadhesive at an angle of 180 degrees at, e.g., 12 in/min (30.5 cm/min).The average force required to peel three liners from the adhesives wasrecorded as the tight side liner release (as grams per inch).

Peel Adhesion Test

The peel adhesion test was performed by the following method. A vaporcoated metalized PET was applied to the transfer tape first. Thenmultiple strips of 2.54 cm wide and approximately 20 cm long sampleswere cut using a specimen razor cutter. At least 3 transfer adhesivetapes with PET backing were applied to a glass adherend, after removingthe liner and then rolling down with a 4.5 lbs roller. Adhered sampleswere aged at 72° F. (22° C.) and 50% RH (CTH) conditions for at least a1 hour dwell time before testing, unless otherwise stated in the resulttable. The strips were peeled from the panel using a peel adhesiontester (IMASS SP-2100 tester, obtained from IMASS, Inc., Accord, Mass.)with a crosshead speed of 12 in/min (30.5 cm/min), unless otherwiseindicated. The peel force was measured, and the panels were observed tosee if visible adhesive residue remained on the panel. The peel data inthe Tables represent an average of three tests.

Preparation of Adhesive Transfer Tapes

Pressure sensitive adhesive compositions were knife-coated onto a paperliner web having a fluoroalkyl silicone release surface. The paper linerweb speed was 2.75 meter/min. After coating, the web was passed throughan oven 11 meters long (residence time 4 minutes total) having threetemperature zones. The temperature in zone 1 (2.75 meter) was 57° C.;temperature in zone 2 (2.75 meter) was 80° C.; temperature in zone 3(about 5.5 meter) was 93° C. The caliper of the dried adhesive wasapproximately 2.5-3.0 mils thick. The adhesive transfer adhesive tapeswere then stored at ambient conditions.

Multi-Layer Composite Tape Preparation

For shear and package weight claim, the transfer adhesives of theexample set were laminated to film-foam-film composites and the desiredsize and geometry was die cut. In specific, the test adhesivecomposition was adhered to the both sides of a composite film-foam-filmconstruction like that found on COMMAND strip products (31 mil 6 lb.foam with 1.8 mil polyethylene film on both sides of the foam). Bothsides of the film-foam-film construction were previously primed with 3MAdhesion Promoter 4298UV (3M Company, St. Paul, Minn.) prior to adhesivelamination.

Samples of the adhesive coated film-foam-film composites were die cut0.5 in×0.5 in (1.27 cm×1.27 cm) for shear testing, or ⅝ in×2 in (1.59cm×5.08 cm) for package weight claim testing.

Copolymers and Adhesive Compositions Silicone Polyoxamide CopolymersExample 1 Preparation and Characterization of Silicone Polyoxamide UsingBTFEO in EtOAc Solution

A 3 gallon jacketed stainless steel reactor equipped with mechanicalstirrer, argon inlet, thermocouple and dip tube was charged with EtOAc(3972.90 g) and BTFEO (54.55 g). The reactor was placed under positiveAr pressure through large oil bubbler and stirred at room temperature.While stirring a 13 k PDMS diamine was charged (AEW=6630 g/mol, 1699.88g, 256.4 mmol of —NH₂). The reactor was sealed and stirred at roomtemperature for 1 h, at which time full consumption of BTFEO wasconfirmed by gas chromatography. The jacket temperature was thenincreased to 70° C. for 30 min, then AcOH (0.1945 g) and EDA (5.0735 g)were added. Reactor was sealed under Ar atmosphere and held at a jackettemperature of 70° C. for 66 h at which time significant increase inviscosity of the reaction mixture was observed. A sample of theresulting polymer was determined to have an IV of 1.08 dL/g (0.2 g/dL inEtOAc, 27° C.).

Examples 2-6

Novel silicone polyamide copolymers were prepared according to Example 1using different starting PDMS diamine amine equivalent weights, amountof catalyst, and relative stoichiometry as outlined in Table 1.

TABLE 1 Silicone Polyamide Copolymers Soft PDMS ppm PDMS Segment PDMSDiamine:Hard total AcOH Diamine MW Length Diamine:Oxalate Segmentamine:total (with (nominal) (nominal) ester Diamine ester respect toExample (g/mol) (g/mol) (mole ratio) (mole ratio) (mole ratio) EtOAc) IV2 13k 20k 0.60 0.66 0.976 24 1.08 3 13k 20k 0.60 0.66 0.982 499 1.04 415k 20k 0.56 0.77 0.967 50 1.05 5 15k 20k 0.56 0.77 0.986 50 0.97 6 15k20k 0.56 0.79 1.014 50 1.07

Example 7

A 3 gal jacketed stainless steel reactor equipped with mechanicalstirrer, argon inlet, thermocouple and dip tube was charged with EtOAc(5184 g) and BTFEO (71.3245 g). The reactor was placed under positive Arpressure through large oil bubbler and stirred at room temperature.While stirring a 13 k PDMS diamine was charged (AEW=6515 g/mol, 2200.80g, 337.78 mmol of —NH₂). The reactor was sealed and stirred at roomtemperature for 1 h, at which time full consumption of BTFEO wasconfirmed by gas chromatography, then AcOH (0.259 g) was added. Aportion of this masterbatch was drained into a 32 oz bottle (523.59 g)and EDA was added (8.1276 g of a toluene solution, 15.34 mmol —NH₂). Thebottle was sealed and placed in a Launder-O-Meter (available from AtlasElectric Devices Co., Chicago, Ill.) at 70° C. for 60 h, at which timethe contents were cooled to ambient temperature. Reaction afforded aclear, colorless elastomer solution that was determined to have an IV of1.04 dL/g (0.2 g/dL in EtOAc, 27° C.).

Examples 8-10

Novel silicone polyamide copolymers were prepared according to Example 7targeting different relative stoichiometry to vary amount of chainextension of the PDMS segment (average p=1.33 to 2.32) as outlined inTable 2.

TABLE 2 Silicone polyamide copolymers Soft PDMS ppm PDMS Segment PDMSDiamine:Hard total AcOH Diamine MW Length Diamine:Oxalate Segmentamine:total (with (nominal) (nominal) ester Diamine ester respect toExample (g/mol) (g/mol) (mole ratio) (mole ratio) (mole ratio) EtOAc) IV8 13k 20k 0.60 0.62 0.975 50 1.10 9 13k 25k 0.65 0.51 0.972 50 1.21 1013k 30k 0.69 0.42 0.975 50 1.22

Example 11

A 12 L resin kettle was charged with BTFEO (94.60 g) and EtOAc (5962 g)under positive nitrogen pressure. The reaction mixture was stirred atroom temperature and 10 k PDMS diamine (AEW=5273 g/mol, 2553 g, 484.13mmol —NH₂) was added over a period of 70 min. After addition wascomplete, the reaction mixture was stirred at room temperature for 2 h45 min, at which time full consumption of BTFEO was confirmed by gaschromatography. A portion of this masterbatch was added to a 32 ozbottle (579.25 g) and EDA was added (8.6149 g of a toluene solution,17.11 mmol —NH₂). The bottle was sealed and placed in a Launder-O-Meter(available from Atlas Electric Devices Co., Chicago, Ill.) at 70° C. for36 h, at which time the contents were cooled to ambient temperature.Reaction afforded a clear, colorless elastomer solution that wasdetermined to have an IV of 1.09 dL/g (0.2 g/dL in EtOAc, 27° C.).

Example 12

A 3 gal jacketed stainless steel reactor equipped with mechanicalstirrer, argon inlet, thermocouple, HYDRAMOTION vibrational viscometer,and dip tube was charged with EtOAc (4331.69 g) and BTFEO (59.9026 g).The reactor was placed under positive Ar pressure through large oilbubbler and stirred (200 rpm) at room temperature. While stirring a 13 kPDMS diamine was charged (AEW=6564 g/mol, 1855.03 g, 282.59 mmol of—NH₂). The reactor was sealed and stirred at room temperature for 1 h,at which time full consumption of BTFEO was confirmed by gaschromatography. The jacket temperature was then increased to 70° C. for1 h, then AcOH (0.2119 g) and EDA (5.6623 g) were added. Reactor wassealed under Ar atmosphere and held at a jacket temperature of 70° C.while in process viscometry measurements were taken. After 3 h and 45min the in-process viscometer read 850 units and additional EDA wascharged (0.3933 g). Stir rate was decreased (96 rpm) and batch wasallowed to cool to room temperature overnight. Reaction afforded aclear, colorless elastomer solution that was determined to have an IV of0.953 dL/g (0.2 g/dL in EtOAc, 27° C.).

Pressure Sensitive Adhesive Formulations from Silicone PolyoxamidesExamples 13-22

Silicone polyoxamide elastomers were prepared and isolated according toExample 1 or 11 and prepared as outlined in Table 3. The siliconepolyoxamide elastomer was combined with MQ resin (Momentive SR-545, 63%in toluene) such that the elastomer/MQ ratio was 50/50 (w/w dry solids)and diluted such that the overall solids content was 35% and the solventblend was a 76/24 (w/w) of EtOAc/IPA. Shear, Liner Release and PeelAdhesion data were obtained according to the test methods describedabove. The data is summarized in Tables 4-6.

TABLE 3 PSA Composition PSA Elastomer Example Example 13 1 14 2 15 3 164 17 5 18 6 19 7 20 8 21 9 22 10

TABLE 4 Shear Data Shear CTH Shear CTH Shear CTH Shear CTH Shear CTHShear CTH on FEN on FEN on FEN on Glass on glass on glass PSA Elastomer(min) (min) (min) (min) (min) (min) Example Example Initial 2 wk 6 wkInitial 2 wk 6 wk 13 1 >28587 14 2 >28587 15 3 >28587 16 4 >116881 3024017 5 >119730 36000 18 6 >116879 >30240 19 7 >25000 329 413 653 109 34220 8 >23890 295 309 1499 132 415 21 9 4973 114 224 1142 107 188 22 10606 163 133 764 140 275

TABLE 5 Liner Release Data Liner Liner Liner Liner Liner Liner releasein release in release in release in release in release in grams gramsgrams grams grams grams (Tight side) (Tight side) (Tight side) (Tightside) (Tight side) PSA Elastomer (Tight side) 2 wk aged 4 wk aged 6 wkaged 4 wk aged 6 wk aged Example Example Initial in 120 F. in ambient inambient at 120 F. in 120 F. 13 1 14 24 14 2 10 20 15 3 9 19 16 4 21 1413 20 17 5 18 15 13.6 20 18 6 57 53 58.3 75 19 7 23 191 294 20 8 73 203308 21 9 105 307 381 22 10 123 263 426

TABLE 6 Peel Adhesion Data Peel Adhesion PSA Elastomer (24 hr dwellExample Example on glass) 13 1 50.3 14 2 46.1 15 3 47.3 16 4 33.1 17 539.0 18 6 55.3 19 7 N.T. 20 8 N.T. 21 9 N.T. 22 10 N.T.

Comparative Example 1

A 16 oz jar with magnetic stir bar was charged with BTFEO (2.73 g) andEtOAc (176.73 g). The jar was stirred at room temperature and 13 k PDMSdiamine (AEW=6592.1 g/mol, 75.81 g, 11.50 mmol —NH₂) was added portionwise. After addition was complete, the jar was sealed and stirred atroom temperature for 1 h. Incomplete consumption of BTFEO was confirmedby gas chromatography. The jar was then opened and AcOH (85 μL) and EDA(2.6790 g of a toluene solution, 9.98 mmol —NH₂) were added. The jar wassealed and placed on roller for 3 d. Reaction afforded a slightly hazy,highly elastic elastomer solution that was determined to have an IV of1.36 dL/g (0.2 g/dL in EtOAc, 27° C.).

The complete disclosures of the publications cited herein areincorporated by reference in their entirety as if each were individuallyincorporated. Various modifications and alterations to this disclosurewill become apparent to those skilled in the art without departing fromthe scope and spirit of this disclosure. It should be understood thatthis disclosure is not intended to be unduly limited by the illustrativeembodiments and examples set forth herein and that such examples andembodiments are presented by way of example only with the scope of thedisclosure intended to be limited only by the claims set forth herein asfollows.

1. A method of making a copolymeric material comprising at least tworepeat units of formula I′:

wherein: each R¹ is independently an alkyl, haloalkyl, aralkyl, alkenyl,aryl, or aryl substituted with an alkyl, alkoxy, or halo; each Y isindependently an alkylene, aralkylene, or a combination thereof, each Gis independently a bond or a divalent residue equal to a diamine offormula R³HN-G-NHR³ minus the two —NHR³ groups; each R³ is independentlyhydrogen or alkyl or R³ taken together with G and with the nitrogen towhich they are both attached form a heterocyclic group; each n isindependently an integer of 0 to 300; each p is independently an integerof 1 to 25; and each q is independently an integer of 1 to 2, and theaverage of q is no greater than 1.05 the method comprising: (a) addingan oxalate ester of formula II to a solvent

wherein: each R² is independently an alkyl, haloalkyl, aryl, or arylsubstituted with an alkyl, alkoxy, halo, alkyoxycarbonyl, or

 bound through the N, wherein each R⁴ is independently hydrogen, alkyl,or aryl or R⁴ taken together form a ring; (b) reacting the oxalate esterwith a polydiorganosiloxane diamine of formula III until essentially nopolydiorganosiloxane diamine or oxalate ester remains

 to form the reaction product of formula IV

 and (c) adding one or more diamines of formula V to the reactionproduct of formula IV to form the repeat unit of formula I′


2. The method of claim 1, wherein the oxalate ester of formula II isselected from the group consisting of oxalate esters of phenol, methylethyl ketone oxime, acetone oxime, and trifluoroethanol.
 3. The methodof claim 1, wherein the solvent is selected from the group consisting oftetrahydrofuran, methyl tert-butyl ether, toluene, ethyl acetate,dichloromethane, and chloroform.
 4. The method of claim 1, wherein thepolydiorganosiloxane diamine of formula III has a number averagemolecular weight of about 1000 g/mol to about 20,000 g/mol. 5.(canceled)
 6. The method of claim 1, wherein the molar ratio of oxalateester of formula II to polydiorganosiloxane diamine of formula III is atleast 1:0.56.
 7. The method of claim 1, wherein the oxalate ester offormula II is fully consumed upon reacting with the polydiorganosiloxanediamine of formula III.
 8. The method of claim 1, wherein the method isperformed in the presence of a protic acid catalyst, wherein thecatalyst comprises acetic acid. 9-10. (canceled)
 11. The method of claim1, wherein the copolymer of formula I′ includes at least than 93 weightpercent polydiorganosiloxane segments p based on the weight of thecopolymer.
 12. (canceled)
 13. The method of claim 1, wherein the diamineof formula V is selected from the group consisting of 1,2-diaminoethane,1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane,2-methyl-1,5-pentanediamine, 1,6-diaminohexane, and m-xylylenediamine.14. The method of claim 1, wherein the molar ratio ofpolydiorganosiloxane diamine of formula III to the diamine of formula Vis less than or equal to about 1:0.8.
 15. The method of claim 1, whereinthe molar ratio of the polydiorganosiloxane diamine of formula III tothe diamine of formula V to the oxalate ester of formula II is about0.6:0.4:1.
 16. (canceled)
 17. The method of claim 1, wherein each R¹ ismethyl, wherein each Y is an alkylene having 1 to 10 carbon atoms,phenylene bonded to an alkylene having 1 to 10 carbon atoms, orphenylene bonded to a first alkylene having 1 to 10 carbon atoms and toa second alkylene having 1 to 10 carbon atoms, wherein G is an alkylene,heteroalkylene, arylene, aralkylene, or a combination thereof, andwherein each R³ is hydrogen. 18-21. (canceled) 22-25. (canceled)
 26. Acopolymeric material comprising at least two repeat units of formula I:

wherein: each R¹ is independently an alkyl, haloalkyl, aralkyl, alkenyl,aryl, or aryl substituted with an alkyl, alkoxy, or halo; each Y isindependently an alkylene, aralkylene, or a combination thereof, each Gis a divalent residue equal to a diamine of formula R³HN-G-NHR³ minusthe two —NHR³ groups; each R³ is independently hydrogen or alkyl or R³taken together with G and with the nitrogen to which they are bothattached form a heterocyclic group; each n is independently an integerof 0 to 300; each p is independently an integer of 1 to 25, and theaverage of p is 1.3 or greater; and each q is independently an integerof 1 to 2, and the average of q is 1.05 or less.
 27. The copolymer ofclaim 25, wherein the copolymer of formula I includes at least than 93weight percent polydiorganosiloxane segments p based on the weight ofthe copolymer.
 28. The copolymer of claim 26, wherein the copolymer offormula I′ includes at least than 95 weight percent polydiorganosiloxanesegments p based on the weight of the copolymer.
 29. The copolymer ofclaim 25, wherein the number average molecular weight of thepolydiorganosiloxane segments p is between about 10,000 g/mol and about25,0000 g/mol.
 30. An adhesive composition, comprising the copolymer ofclaim 25, a silicate tackifying resin, and optionally inorganic particlefiller. 31-32. (canceled)